Lubricant additive and composition containing same



United States Patent 3,073,780 LUBRICANT ADDITIVE AND COMPOSITION CONTAINING SAME Albert R. Sabol, Munster, Hurley D. Cook, Highland, and Robert E. Karll, Munster, Ind., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Filed Sept. 4, 1958, Ser. No. 758,925

17 Claims. (Cl. 252-323) The present invention relates to an improved lubricant additive and lubricant compositions containing the same for meeting requirements of current internal combustion engine lubrication.

Neutralized reaction products of a phosphorous sulfide and a hydrocarbon, particularly olefin polymer, are widely used as detergent-type additives in lubricants, especially in crankcase lubricating oils of internal combustion engines. The use of such additives in lubricant compositions is described in US. Patents No. 2,316,080 and No. 2,316,082, issued April 6, 1943, to C. M. Loane et al. Such detergent-type additives are most effective under heavy duty, high temperature conditions of engine operation. However, in engines operating under moderate or light duty service and under intermittent operating conditions, wherein low engine jacket and crankcase temperatures prevail, such detergent additives often are of limited effectiveness in combating sludge conditions of the low-temperature type which may result from extreme oil contamination with combustion chamber blow-by products. For such low-temperature operating conditions lubricant detergent-type additives of high ratios of alkaline.

earth metal to detergent phosphorous are desired. Also, it is desirable to provide a low-temperature detergent-type additive which is elfective in preventing the corrosion of copper and silver which are components of bearings, etc. in present day internal combustion engines.

It is an object of the present invention to provide a method of preparing an improved lubricating oil low-temperature detergent-type additive having a high alkaline earth metal to detergent phosphorous ratio. Another object is to provide a lubricating oil additive having a high alkaline earth metal to detergent phosphorus ratio and which possesses improved detergency and bearing cor rosion inhibiting properties. Another object of this invention is to provide as an additive a phosphorous acidcontaining alkaline earth-neutralized reaction product of a phosphorus sulfide and a hydrocarbon having a high alkaline earth content, which additive has improved detergency and corrosion-inhibiting properties. Still another object of the invention is to provide a lubricant composition containing the improved additive. Other objects and advantages of the invention will become apparent from the following description thereof.

In accordance with the present invention, the foregoing objects are attained by the use of an oil-soluble additive complex obtained by reacting a phosphorus sulfide, e.g. phosphorus pentasulfide, with a high-boiling hydrocarbon, as hereinafter described, hydrolyzing the resultant reaction product, and subsequently forming a complex by reacting the hydrolyzed reaction product with an inorganic phosphorus acid and a basic alkaline earth compound in the presence of water and an alkanol of 1 to 3 carbon atoms or water and a mixture of such alkanols and a phenol or an alkylated phenol having from about 5 to about 12 carbon atoms in the alkyl group or groups under the hereinafter described conditions. The resulting products are used in lubricating oils as detergent-type corrosioninhibiting additives in concentrations of from .002 to 15 weight percent and may be used in additive concentrates in amounts greater than 15 weight percent and preferably less than 50 weight percent.

In the preparation of the phosphorus sulfide-hydrocarbon reaction products, the hydrocarbon is reacted withv carbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or isomonoolefinic hydrocarbons, such as butylenes or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins or mixtures of olefins in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts type.

The polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isornono-olefin polymers from about 150 to about 50,000 or more, and preferably from about 300 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing mono-olefins and isomono-olefins such as butylene and isobutylene at atemperature of from about F. to about F. in the presence of a metal halide catalyst of the Friedel- Crafts types such as, for example, boron fluoride, alumminum chloride, and the like. In the preparation of these polymers, we may employ, for example, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufac-- ture of gasoline.

Essentially parafiinic hydrocarbons such as bright stock residuums, lubricating oil distillates, petrolatums, or paraffin waxes, may be used. There can also be employed the. condensation products of any of the foregoing hydrocarbons, usually formed by first halogenating the hydro. carbons and then condensing with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride, and. the like.

Other preferred olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins can be obtained by the dehydrogenation of parafiins, such as by the cracking of paraffin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paraffin waxes.

The phosphorus sulfide-hydrocarbon reaction product is prepared by reacting the phosphorus sulfide, e.g. P 8 with the hydrocarbon at a temperature of from about. 200 F. to about 600 F., preferably from about 300 F. to about 500 F., using from 1% to about 50%, preferably from about 5% to about 25% of phosphorus sulfide; the reaction is carried out in from about one to about ten hours. It is preferable to use an amount of the phosphorus sulfide that will completely react with the hydro carbon so that no further purification is necessary; however, an excess of the phosphorus sulfide can be used, and the unreacted material separated by filtration. The reaction, if desired, can be carried out in the presence of a sulfurizing agent such as sulfur or a halide of sulfur as described in US. 2,316,087, issued to J. W. Gaynor Patented Jan. 15., 1963 having molecular weights ranging y 7 3 et a1. April 6, 1943. It is advantageous to maintain a non-oxidizing atmosphere, for example an atmosphere of nitrogen, in the reaction vessel. The reaction product obtained is then hydrolyzed at a temperature of from about 200 F. to about 500 F., preferably at a temperature of about 300 F.-400 F. by suitable means, such as for example, by introducing steam through the reaction mass. The hydrolyzed product, containing inorganic phosphorus acids formed during the hydrolysis can be used as such in the subsequent neutralization stage; or it can be substantially freed of the inorganic phosphorus acids by contacting with an adsorbent material such as Attapulgus clay, fullers earth and the like at a temperature of 100 F.-500 F. as fully described and claimed in US. 2,688,612, issued to R. Watson on September 7, 1954, or by extraction with phenol or an alkanol of 1 to carbon atoms in admixture with water as described and claimed in US. 2,843,579, issued to N. E. Lemmon et al. on July 15, 1958.

The additive compositions of our present invention are prepared by neutralizing a hydrolyzed phosphorus sulfidehydrocarbon reaction product, which may be formed, for example, by the above recited process, and complexing with an alkaline earth compound in the presence of an inorganic phosphorus acid, a mono-hydroxy compound and water. The hydrolyzed reaction product is neutralized by the basic alkaline earth compound which may be a compound such as, for example, the oxide, hydroxide, carbonate or sulfide of calcium, barium, strontium or magnesium, although barium oxide is preferred. The monohydroxy compound is an alkanol having from 1 to 3 carbon atoms or a mixture of such alkanol and a phenol or an alkylated phenol such as, for example, methanol, ethanol, propanol and isopropanol and mixtures of these alkanols with such phenolic compounds as phenol, amyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, etc., of which methanol or a mixture of methanol and nonyl phenol are preferred. The neutralization of the hydrolyzed phosphorus sulfide-hydrocarbon reaction product in the presence of the inorganic phosphorus acid, alkanol and water is carried out at the reflux temperature of the alkanol or alkanol mixture, namely a temperature corresponding to from about 155 F. to about 185 F. at atmospheric pressure. The inorganic phosphorus acid is preferably used in the form of the acid compound such as phosphorous acid, phosphoric acid and hypophosphorous acid, although phosphorus acid producing compounds such as phosphorus oxides and phosphorus halides, which readily hydrolyze to acids, and esters which easily dissociate to acids may also be used. We prefer to phosphorus acids such as phosphoric acid, phosphorous acid and hypophosphorous acid.

The formation of the complex can be carried out directly with the phosphorus sulfide-hydrocarbon reaction product; however, to facilitate handling, it is preferable to form a solution of the hydrolyzed phosphorus sulfidehydrocarbon reaction product in a lubricating oil, such as for example, a SAE 5W oil, although any suitable normally liquid hydrocarbon or oil diluent can be used.

The complex is suitably formed by adding to the oildiluted hydrolyzed phosphorus sulfide-hydrocarbon reaction product from about 0.10 mole to about 1.0 mole of the inorganic phosphorus acid per 1 mole of organic phosphorus and neutralizing the mixture with from about 1.25 moles to about 2.5 moles of the basic alkaline earth compound per mole of organic phosphorus in the presence from about 0.4 mole to 2 moles water and from about 3 moles to about moles of the alkanol, or the mixture of said alkanol and from about 0.1 mole to about 1.0 mole of phenol or alkylated phenol, per mole of the basic alkaline earth compound, and heating the reaction mixture at reflux conditions of the alkanol for a period of from about 1 hour to about 10 hours. When using a mixture of said monohydroxy compounds, the alkanol and phenol compound are used in the ratio of from about 2:1 to about 1021. The reaction vessel is equipped with a reflux condenser to avoid the loss of alkanol, phenol and water vapors. After heating under reflux conditions for the required time, the refluxed mixture is raised to a temperature corresponding to about 200 F.400 F., preferably 212 F.-240 F., at atmospheric pressures, the alkanol, excess phenol, and water distilled off, and the resultant neutralized complex recovered, such as by filtering through a suitable absorbent material such as for example Celite, Attapulgus clay, fullers earth and the like. Naturally, all of the above temperature ranges may be varied with higher or lower pressures and such variances are to be considered within the scope of our invention.

The following specific examples illustrate the preparation of the herein described additive complex. It is to be understood that the examples are for the purpose of illustration only and are not to be regarded as a limitation of the present invention.

HY DROLYZED INTERMEDIATE A butene polymer having an average molecular weight in the range of about 750 to 800 was reacted with 15.5 wt. percent P S at a temperature of about 450 F. for a period of about 5 /2 hours. The product was then hydrolyzed with steam at a temperature of about 400 F. until the acidity of the product remained substantially constant with continued steaming. The reaction product was diluted with an equal volume of an SAE 5 base oil. The diluted, hydrolyzed product had an acid number of about 38 and a total phosphorus content of 2.52%.

Example I 1,500 g. of the hydrolyzed intermediate having 1.22 moles of phosphorus was mixed with 0.28 mole of H PO and diluted with 700 g. of a SAE 5W mineral lubricating oil. The diluted mixture was neutralized with 2.2 moles of barium oxide in the presence of 0.8 mole of water per mole of barium oxide and 5 moles of methanol per mole of barium oxide. The neutralization mixture was heated to F. (the' reflux temperature of the methanol) for 3 hours and the resulting product was then heated to 300 F. and filtered through Celite. The filtered product contained 1.78% phosphorus and 10.76 barium and had a barium to phosphorus ratio of about six to one.

Example 11 1,500 g. of the hydrolyzed intermediate having 1.22 moles of phosphorus was mixed with 0.5 mole of H PO and diluted with 1500 g. of a SAE 5W mineral lubricating oil. The diluted mixture was neutralized with about 2.7 moles of barium oxide in the presence of 0.2 mole of nonyl phenol per mole of barium oxide, 5 moles of methanol per mole of barium oxide and 0.8 mole of water per mole of barium oxide. The neutralization mixture was reacted at 158 F. (at reflux temperature) for three hours and filtered at 350 F. The filtered product contained 1.34% phosphorus, 10.31% barium and had a barium to phosphorus ratio of about 7.7 to 1.

Example III 1,500 g. of the hydrolyzed intermediate having 1.22 moles phosphorus was mixed with 0.4 mole of H PO after dilution with 1,500 g. of a SAE 5W mineral lubricating oil. The diluted mixture was neutralized with 2.2 moles of barium oxide in the presence of 5 moles of methanol per mole of barium oxide and 0.8 mole of water per mole of barium oxide at 158 F. for three hours. The resulting product was heated to 350 F. and filtered. The filtered product contained 1.4% phosphorus and 8.22 barium and had a barium to phosphorus ratio of about 5.87 to 1. a

' Example IV 1,000 g. of the hydrolyzed intermediate having 0.81 mole of phosphorus was mixed with 0.66 mole of H PO after dilution with 1,000 g. of a SAE W mineral lubricating oil. The diluted mixture was neutralized with 1.6 mole of barium oxide with the presence of 0.8 mole of water per mole of barium oxide and 5 moles of methanol per mole of barium oxide at 158 F. (the methanol reflux temperature) for three hours. The resulting product was heated to 350 F. and filtered to obtain a product containing 1.6% phosphorus and 8.7% barium and having a barium to phosphorus ratio of 5.4 to 1.

Example V 1,740 g. of a hydrolyzed intermediate containing 2.40% phosphorus were diluted with 1,330 g. of a SAE 5W mineral lubricating oil. The diluted reaction product containing 1.35 moles of phosphorus was mixed with 0.65 mole of H PO and the mixture was neutralized with 3.2 moles of calcium oxide in the presence of one mole of water per mole of calcium oxide and 5 moles of methanol per mole of calcium oxide at 158 F. (the methanol reflux temperature) for three hours. The product was heated to 350 F. and filtered. The filtered product contained 2.01 calcium and 1.61% phosphorus and had a calcium to phosphorus ratio of about 1 to 1.

Example VI An amount of the hydrolyzed intermediate containing 25.7 g. of phosphorus was diluted to 1.26% phosphorus with a SAE 5W mineral lubricating oil. The diluted reaction product was mixed with 44 g. of hypophosphorus acid and neutralized with 250 g. barium oxide in the presence of 0.8 mole of water per mole ofbarium oxide and 5 moles of methanol per mole of barium oxide at reflux temperature for about three hours. The resulting product was heated to drive off methanol and water and was filtered. The final filtered product contained 1.6% phosphorus and 8.6% barium and had a'viscosity of 154 SSU at 210 F. and a barium to phosphorus ratio of about 5.4 to 1.

The low-temperature detergency property of the complex of the present invention is demonstrated by the data in Table I, below, which data were obtained in the engine test designed to determine the low temperature detergency of motor oils. The test, known as the L-l test, having C.R.C. designation L-1-545 is fully described in C.R.C. Handbook, 1946 edition, of the Coordinating Research Council, New York. Briefly, the test is conducted in a 1A-S1 single cylinder Caterpillar engine operating at 1,000 rpm. at a load of 19.8 B.H.P. with an oil temperature to bearings of 145 -150 F. and a water jacket outlet temperature of 175-180 F. and an inlet temperature of 15 F. below the outlet temperature. The test is run for 480 hours, with inspections at the end of 120, 240 and 480 hour periods for carbon in the ring grooves, expressed in terms of percent groove filled.

' The following lubricant composition samples were subjected to the above test and the data in Table I were obtained.

Sample A-SAE 30 base motor oil containing 6.8% of a barium oxide neutralized hydrolyzed reaction product of a polybutene of about 780 molecular weight and P 8 and 0.79% of sulfurized dipentene.

Sample B-SAE 30 base motor oil containing 5.5% of the product of Example 111 (phosphorus equivalent to 5.5% of the barium neutralized hydrolyzed polybutene-P S reaction product of sample A) and 0.79% of sulfurized dipentene.

Sample C-SAE 30 base motor oil containing 5.5 of a barium oxide neutralized hydrolyzed reaction product of a polybutene of about 780 molecular weight and P 5 and 0.625% of a zinc dialkyl dithiophosphate.

Sample D-SAE 30 base motor oil containing 5.5% of the product of Example V and 0.625% of a zinc dialkyl dithiophosphate.

TABLE LRESULTS OF L-l ENGINE TEST Detergency Percent Top Ring Groove Carbon Sample Level 240 Hrs. 480 Hrs.

S-l 22 27 S1 8 22 S1 8 18 S1 a. 5 6

In each of the tests, the lacquer was zero percent. In the L-l test, a carbon value of less than 25% is passing.

The herein described additive compositions of the present invention can be used as indicated above in varying amounts of from .002 up to about 15% in lubricating oils. Although the present invention has been illustrated by the use of the additive compositions in mineral lubricating oils, it is not restricted thereto. Other lubricating oil bases can be used, such as hydrocarbon oils, both natural and synthetic for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type and the polycarboxylic acid ester type, such as the oil soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other well known additives, such as antioxidants, anti-foaming agents pourpoint depressors, extreme pressure agents, antiwear agents, may be incorporated in lubricating oils containing the additives of our invention.

Concentrates of a suitable oil base containing more than 15 percent, for example up to 50 percent or more, of the additives of this invention alone or in combination with other additives can be used for blending with hydrocarbon oils or other oils in the proportions desired for the particular conditions of use to give a finished lubricating product containing the additives of this invention.

Unless otherwise stated, the percentages given herein and in the claims are percentages by weight.

Although we have described our invention by reference to specific embodiments and examples thereof, such specific embodiments and examples as have been given are merely for the purpose of illustration of the invention and are not intended as limiting its scope. It is intended that modifications and variations of the present invention which are apparent from our foregoing description to those skilled in the art are to be considered within the scope of our present invention except as stated in the following appended claims.

We claim: I v

'1. As a new composition of matter, an oil soluble neutralized complex prepared by the process comprising reacting a high boiling hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., hydrolyzing the resultant phosphorus sulfideahydrocarbon'reaction product at a temperature in the range of 200 F. to 500 F., and reacting the hydrolyzed product at a temperature between F. and 400 F. with from. about 0.1 to about one mole of added inorganic phosphorus acid per mole of phosphor-us present in the hydrolyzed product and a basic alkaline earth compound, water and from about 3 to 10 moles per mole of alkaline earth compound of a watersoluble anonohydroxy compound selected from the group line earth compound is a basic barium compound.

3. The composition of claim 1 wherein the basic alkaline earth compound is a basic calcium compound.

4. The composition of claim 1 wherein the inorganic phosphorus acid is phosphorous acid.

5. The composition of claim 1 wherein the inorganic phosphorus acid is hypophosphorous acid.

6 The composition of claim 1 wherein the phosphorus sulfide is phosphorus pentasulfide and the hydrocarbon is a butene polymer.

7. The composition of claim 1 where the water-soluble monohydroxy compound is a mixture of, nonyl phenol with methanol.

8. The composition of claim 1 containing added diluent before neutralization with the basic alkaline earth compound.

9. A lubricant composition comprising a major proportion of a normally liquid lubricating oil and from about .002 to about 15% of the composition of claim 1.

10. As a new composition of matter, an oil-soluble neutralized complex prepared by the process comprising reacting a high boiling hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction prodnot, treating the hydrolyzed product with from about 0.1 to about 1.0 mole of added inorganic phosphorus acid per mole of phosphorus present in the hydrolyzed product, and neutralizing the resulting mixture at a temperature of from about 155 F. to about 185 F. with from about 1.25 to about 2.5 moles of a basic alkaline earth compound per mole of phosphorus present in said hydrolyzed prodnot, water and a water-soluble monohydroxy compound selected from the group consisting of an alkanol of from 1 .to about 3 carbon atoms and mixtures of an alkanol having from 1 to about 3 carbon atoms with a phenol selected from phenol and an alkylated phenol having from about 5' to about 12 alkyl carbon atoms, under refiux conditions.

11. The composition of claim wherein the basic alkaline earth compound is barium oxide.

12. The composition of claim 10 wherein the basic alkaline earth compound is calcium oxide.

13. The composition of claim 10 wherein the watersoluble monohydroxy compound is methanol.

14. A lubricant composition comprising a major proportion of a normally liquid mineral lubricating oil and from about .002% to about 15% of the composition of claim 10.

15. As a new composition of matter, an oil soluble neutralized complex prepared by the process comprising reacting a high boiling hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature of} from about 200 F. to about 600 F., hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction prodnot, treating the hydrolyzed product with from about 0.1 to about 1.0 mole of added inorganic phosphorus acid per mole of phosphorus present in said hydrolyzed product, and neutralizing the resulting mixture of hydrolyzed product and inorganic phosphorus acid with from about 1.25 to about 2.5 moles of a basic alkaline earth oxide per mole of phosphorus present in said hydrolyzed product in the presence of from about 0.4 to about 2 moles of water per mole of basic alkaline earth oxide and from about 3 moles to about 10 moles, per mole of basic alkaline earth oxide, of a water-soluble monohydroxy compound selected from the group consisting of an alkanol of, from 1 to about 3 carbon atoms and mixtures of an alkanol having from 1 to about 3 carbon atoms with a phenol selected from phenol and an alkylated phenol having from about 5 to about 12 alkyl carton atoms, said mixtures having an alkanol to phenol ratio of from 2 to 1 to 10 to 1, under reflux conditions of the monohydroxy compound.

16. An addition agent concentrate for lubricating oil comprising essentially a major proportion of a lubricating oil containing more than about 15% of an oil soluble neutralized complex capable of dilution with a lubricating oil to a concentration in the range of fram about .002 to about 15% of said oil soluble neutralized complex being prepared by the process comprising reacting a high boiling hydrocarbon with from about 1% to about 50% of a phosphorus sulfide at a temperature of fram about 200 F. to about 600 F., hydrolyzing the resultant phosphorus sulfide-sydrocarbon reaction product and neutralizing the hydrolyzed product with a basic alkaline earth compound in the presence of an inorganic phosphorus acid, water and a water-soluble monohydroxy compound selected from the group consisting of an alkanol of from 1 to about 3 carbon atoms and mixtures of an alkanol having from 1 to about 3 carbon atoms with a phenol selected from phenol and an alkylated phenol having from about 5 to about 12 alkyl carbon atoms.

17. As a new composition of matter, an oil soluble neutralized complex prepared by the process comprising reacting a butene polymer with from about 1% to about 50% of a phosphorus sulfide at a temperature of from about to about 600 F., hydrolyzing the resulting reaction product at a temperature of from about 200 F. to about 500 F., treating the hydrolyzed reaction product with from about 0.1 to about 1.0 mole, per one mole of phosphorus contained in the hydrolyzed reaction product, of an inorganic phosphorus acid to form a reaction mixture, neutralizing the reaction mixture at a temperature in the range of from about F. to about F. with from about 1 to about 4 moles of barium oxide per mole of phosphorus in said reaction product in the presence of from about 0.2 to about 2.0 moles of water per mole of barium oxide and from about 1 to about 10 moles of methanol per mole of barium oxide for a period of time of from about 1 to about 10 hours under methanol reflux conditions.

References Cited in the file of this patent UNITED STATES PATENTS 2,688,612 Watson Sept. 7, 1954 2,799,653 Scanley July 16, 1957 2,806,022 Sabol Sept. 10, 1957 2,900,376 Sabol et al Aug. 18, 1959 

1. AS A NEW COMPOSITION OF MATTER, AN OIL SOLUBLE NEUTRALIZED COMPLEX PREPARED BY THE PROCESS COMPRISING REACTING A HIGH BOILING HYDROCARBON WITH FROM ABOUT 1% TO ABOUT 50% OF A PHOSPHORUS SULFIDE AT A TEMPERATURE OF FROM ABOUT 200*F. TO ABOUT 600* F, HYDROLZING THE RESULTANT PHOSPHORUS SULFIDE-HYDROCARBON REACTION PRODUCT AT A TEMPERATURE IN THE RANGE OF 200*F. TO 500*F., AND REACTING THE HYDROLYZED PRODUCT AT A TEMPERATURE BETWEEN 155* F. AND 400 F. WITH FROM ABOUT 0.1 TO ABOUT ONE MOLE OF ADDED INORGANIC PHOSPHORUS ACID PER MOLE OF PHOSPHORUS PRESENT IN THE HYDROLYZED PRODUCT AND A BASIC ALKALINE EARTH COMPOUND, WATER AND FROM ABOUT 3 TO 10 MOLES PER MOLE OF ALKALINE EARTH COMPOUND OF A WATERSOLUBLE MONOHYDROXY COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN ALKANOL OF FROM 1 TO ABOUT 3 CARBON ATOMS AND MIXTURES OF AN ALKANOL HAVING FROM 1 TO ABOUT 3 CARBON ATOMS WITH PHENOL SELECTED FROM PHENOL AND AN ALKYLATED PHENOL HAVING FROM ABOUT 5 TO ABOUT 12 ALKYL CARBON ATOMS.
 9. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF A NORMALLY LIQUID LUBRICATING OIL AND FROM ABOUT .002 TO ABOUT 15% OF THE COMPOSITION OF CLAIM
 1. 